CN1238795A - Asphalt modified with olefin/vinylidene aromatic monomer interpolymers - Google Patents

Abstract

Bitumens can be blended with interpolymers prepared from at least one olefin and at least one vinylidene aromatic monomer and, optionally, at least one diene. The interpolymers prepared from monomers containing a diene are new compositions of matter. When the interpolymers prepared from monomers containing a diene are blended with a bitumen, the blends are crosslinkable.

Description

Pitch with alkene/vinylidene aromatic monomer interpolymers modification

Background of invention

The present invention relates to comprise the pitch of the interpolymer modification of using alkene and vinylidene aromatic monomer or the blend composition of bituminous material, its can be used for paving the way, put up a house top and contain other material of construction of said composition the invention still further relates to the method for the described blend composition of preparation and is used to prepare the interpolymer of this blend composition.The invention still further relates to the new random basically interpolymer that obtains by at least a alkene of polymerization, at least a vinylidene aromatic monomer and at least a diolefine.

Petroleum residue such as pitch are known as the purposes of pavior and other material of construction.It also is known that various polymer materialss are sneaked in the pitch to improve some performance.For example, used polyolefine, but as US4, (its disclosed content special here as with reference to introducing) of pointing out in 240,946 adds these polyolefine these blends viscosity when working temperature raise, and therefore needs special mixing and homogenization step.Yet these polyolefine are special needs, bear high temperature because work as pitch, and when paving the way, putting up a house top or other material of construction as being used as, they help to keep the bituminous globality.If the material of finding can make the temperature limit of bituminous material broaden when adding in the bituminous material, bituminous material is hardened when high temperature, keep low temperature flexibility and appropriate viscosity simultaneously, then this needs.If this additive to the bituminous material blend during the high-temperature stable that stands and make that blend is stable for a long time to be stored, then also need.

If can obtain and various bituminous composition compatible polymers, then this is special needs.If these polymkeric substance are only sneaked in the pitch by low shear agitation easily, then this also needs.The present invention's general introduction

The present invention relates to a kind of composition, comprise (A) about 85 to the bituminous material of about 99% weight and (B) the about 1 at least a interpolymer to about 15% weight, described interpolymer contains about 20 and has 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and about 20 to about 80% weight.

The present invention relates to a kind of composition on the other hand, comprise (A) about 90 to the bituminous material of about 99% weight and (B) about 1 at least a ethylene/styrene interpolymer to about 10% weight, described interpolymer contain about 25 to about 60% weight derived to cinnamic polymer unit and about 40 polymer units to the derived from ethylene of about 75% weight.

Further aspect of the present invention relates to a kind of water dispersion or emulsion, comprises to be scattered in the water to form water dispersion or emulsion:

(A) about 90 bituminous material to about 99% weight; With

(B) the about 1 at least a interpolymer to about 10% weight, described interpolymer contain about 20 and have 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and about 20 to about 80% weight.

The invention still further relates to a kind of random basically interpolymer, comprise:

(1) about 30 have 2 polymer units to the alkene of about 10 carbon atoms derived from least a to about 80% weight;

(2) about 20 polymer units derived from least a vinylidene aromatic monomer to about 80% weight; With

(3) about 1 has 4 polymer units to the diolefine of about 10 carbon atoms to about 20% weight derived from least a.

The present invention can comprise following content, by following content form or basically by all or only the following content of part form: component, compound, substituting group or reactions steps.Can deduct in component, compound, substituting group or the reactions steps or deduct wherein any two or multinomial simultaneously.Brief description of the drawings

There is not detailed description of the present invention

Term " alkyl " is meant that aliphatic series, cyclic aliphatic, aromatics, aryl replace aliphatic series, aryl substituted ring aliphatic series, aliphatic group replaces aromatics or cyclic aliphatic replaces aromatic group.Aliphatic series or cycloaliphatic groups are preferably saturated.In addition, term "-oxyl " is meant the alkyl that has oxygen between this group and the carbon atom that is connected it.

Term used herein " interpolymer " is meant wherein will at least two kinds of polymkeric substance that different monomer polymerizations prepares.

Term " random basically " in comprising the random basically interpolymer of alpha-olefin and vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer used herein is meant, monomer distribution Ke Yong Bai Nuli (Bernoulli) statistical model of described interpolymer or with first or second stage Markovian statistical model describe, as J.C Randel at the " C that polymer sequence is measured ¹³-NMR method (POLYMER SEQUENCE DETERMINATION, Carbon-13NMR Method) ", Academic Press New York, 1977, describe among the pp.71-78.Comprise 15% weight that inferior ethene aromatic monomer amount that the random basically interpolymer of alpha-olefin and vinylidene aromatic monomer contains is not more than the vinylidene aromatic monomer total amount in the block more than 3 vinylidene aromatic monomers.More preferably, this interpolymer does not have the isotaxy or the syndiotaxy feature of high level.This means in the 13C-NMR of random interpolymer composes basically, should be no more than 75% of main chain methylene radical and methine carbon atom total peak area corresponding to main chain methylene radical and the methine carbon atom peak area of representing meso diad sequence or racemize diad sequence.

Here any numerical value of quoting comprises all values that increases by unit to high value from than low value, as long as at any interval that has at least 2 units between than low value and high value.For example, be (for example) 1 to 90 if point out the value of the amount of component or method variable such as temperature, pressure, time etc., preferred 20 to 80, more preferably 30 to 70, then mean and in this scope, clearly enumerated numerical value as 15 to 85,22 to 68,43 to 51,30 to 32 etc.For the numerical value that is lower than 1, if suitable 1 unit thinks 0.0001,0.001,0.01 or 0.1.These only are the examples that specifically provides, and think all possible combination that clearly provides the numerical value between Schwellenwert and the maximum in this application in a similar manner.

The composition of the present composition depends on end-use, for example for the top of putting up a house, the present composition comprise (A) about 99 to about 75% weight, preferred about 90 to about 75% weight, 85 bituminous material more preferably from about to about 90% weight; (B) about 1 to about 25% weight, preferred about 10 to about 25% weight, 10 at least a interpolymers more preferably from about to about 15% weight, described interpolymer comprises derived from the polymer unit of at least a vinylidene aromatic monomer with derived from least a having 2 polymer units to the aliphatic olefin of about 20 carbon atoms.

Pave the way for being used to, the present composition comprises (A) about 90 to about 99% weight, 94 bituminous material to about 97% weight more preferably from about; (B) about 1 to about 10% weight, the preferred about 3 at least a interpolymers to about 6% weight, and described interpolymer comprises derived from the polymer unit of at least a vinylidene aromatic monomer with derived from least a having 2 polymer units to the aliphatic olefin of about 20 carbon atoms.Bituminous material

Term " bituminous material " may be defined as natural or the hydrocarbon in pyrolysis source or the mixture of the two combination (usually following its nonmetal derivative) usually, and it can be gaseous state, liquid state, semi-solid state or solid-state, and is dissolved in the dithiocarbonic anhydride usually.For the present invention, can use the bituminous material of liquid state, semi-solid state or solid state properties.From industrial consideration, bituminous material is limited to pitch, tar and wood pitch (pitch) usually.Can be used for a series of various bituminous material of the present invention comprises: I. pitch

1. petroleum pitch

A. straight chain protobitumen also

1. normal pressure or decompression reduction

Solvent, as propane precipitation,

B. pyrolysis pitch is as the resistates to the petroleum cracking operation

C. atmospheric oxidation pitch

1. direct oxidation

2. " catalysis " oxidation

2. rock asphalt

A. have and be lower than 5% mineral content

1. vasphaltic pyrobitumen such as gilsonite, grahamite and manjak

2. Bermuda rock (Bermudez) and other natural sediment

B. have mineral content and surpass 5%

1. the sandstone of bituminous 10% or limestone (rock asphalt)

2. Trinidad asphalt (Trinidad) and other natural sediment II. tar and derivative

1. from the resistates of coke-oven coal tar

A. be reduced to the level of floating, as the RT that is used to pave the way (road tar) level

Coal tar

B. coal-tar pitch reduces and proceeds to the softening temperature level.

From other pyrolysis distillment such as steam, timber, coal slime, bone, shale,

The resistates of rosin and lipid acid

Easily understand as those skilled in the art, the weight-average molecular weight of various bituminous material can change in wide region, and according to appointment 500 to about 10,000.In addition, all kinds bituminous softening temperature also can change, 50 °F to about 400 °F according to appointment.

In spendable broad variety pitch, oil and rock asphalt are suitable, and wherein petroleum pitch is preferred.In petroleum pitch, pyrolysis pitch is preferred.

The interpolymer of alkene and vinylidene aromatic monomer

The interpolymer that is suitable for preparing blend of the present invention includes but not limited to by the interpolymer with one or more alkene and one or more vinylidene aromatic monomer polymerizations preparation.

Suitable alkene comprises that (for example) contains 2 to about 20, preferred 2 to about 12, more preferably 2 those alkene to about 9 carbon atoms.These alkene are preferably alpha-olefin.Specially suitable is following alpha-olefin, as ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1.

Suitable vinylidene aromatic monomer comprises those monomers that (for example) following general formula is represented

R wherein ¹Be selected from hydrogen and contain 1 alkyl, preferred hydrogen or methyl to about 6 carbon atoms; Each R ²Be independently selected from hydrogen and contain 1 alkyl, preferred hydrogen or methyl to about 6 carbon atoms; Ar is phenyl or is selected from halogen, C by 1 to 5 _1-4Alkyl and C _1-4The phenyl that haloalkyl replaces.The example of monovinylidene aromatic monomer comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chloro-styrene, comprises all isomer of these compounds etc.Specially suitable these monomers comprise vinylbenzene and low alkyl group-or its halogen substitutive derivative.Preferred vinylidene aromatic monomer comprises vinylbenzene, alpha-methyl styrene, cinnamic low alkyl group-or phenyl ring substitutive derivative, as adjacent-,-and p-methylstyrene, ring halogenated vinylbenzene, to Vinyl toluene or its mixture.Preferred monovinylidene aromatic monomer is a vinylbenzene.

In some cases, as in the interpolymer of component of the present invention (B), except that alkene and vinylidene aromatic monomer, can use one or more diolefinic monomer suitably in preparation.Specially suitable diolefine comprises the aliphatic diolefine hydrocarbon, as ethylidene norbornene, piperylene, 7-methyl isophthalic acid, and 6-octadiene, 1, the dimer of 4-hexadiene and cyclopentadiene or its any mixture.Preferred diolefinic monomer comprises (for example) ethylidene norbornene, and these monomers also are adapted at being used as in the random basically interpolymer of the present invention diolefinic monomer (component 3).

The interpolymer that is used as component (B) among the present invention contain about 30 to about 80% weight, preferred about 40 to about 75% weight, 50 polymer units more preferably from about derived from olefinic monomer to about 75% weight; About 20 to about 80% weight, preferred about 25 to about 60% weight, more preferably from about 25 to the polymer unit of about 50% weight derived from vinylidene aromatic monomer; With about 0 to about 20% weight, preferred about 2 to about 15 weight %, 5 diolefinic monomer more preferably from about to about 15% weight.

When in preparation the present invention when comprising one or more diolefinic monomer in the interpolymer of component (B), interpolymer use usually (1) about 30 to about 79% weight, preferred about 45 to about 75% weight, 40 one or more alkene more preferably from about to about 70% weight; (2) about 20 to about 70% weight, preferred about 25 to about 45% weight, 25 one or more vinylidene aromatic monomers more preferably from about to about 40% weight; (3) about 1 to about 20% weight, preferred about 2 to about 15% weight, more preferably from about 5 one or more diolefine preparations to about 15% weight.

Being particularly suitable for interpolymer of the present invention is the polymer unit that contains derived from ethylene, derived from the random basically interpolymer of cinnamic polymer unit and non-essential monomeric unit derived from ethylidene norbornene.These interpolymers contain usually (1) about 30 to about 80% weight, preferred about 40 to about 75% weight, 50 ethene more preferably from about to about 75% weight; (2) about 20 to about 80% weight, preferred about 25 to about 60% weight, more preferably from about 25 to the styrene units of about 50% weight and non-essential (3) about 1 to about 20% weight, preferred about 2 to about 15% weight, 5 ethylidene norbornenes more preferably from about to about 15% weight.

When preparing random basically or false random copolymer, as will be described below, component (B) is because therefore vinylidene aromatic monomer homopolymerization at high temperature can form a certain amount of atactic vinylidene aromatic monomer homopolymer.Usually, polymerization temperature is high more, and the amount of the homopolymer of formation is big more.The homopolymer of the vinylidene aromatic monomer that exists is harmless and can allow to the object of the invention usually.If need, this vinylidene aromatic homopolymer can be passed through with suitable extraction agent from component (B), acetone or chloroform extraction are separated.For the present invention, in component (B), preferably there is no more than 20% weight, more preferably less than the vinylidene aromatic monomer homopolymer (by the weight of component (B)) of 10% weight.

The preparation suitable catalyst of random interpolymer and the example of method basically is disclosed in US application serial number 545,403, the July 3 nineteen ninety applying date (EP-A-416,815); US application serial number 702,475, May 20 1991 applying date (EP-A-514,828); US application serial number 876,268, May 1 1992 applying date (EP-A-520,732); US application serial number 241,523, May 12 1994 applying date; And in the United States Patent (USP) 5,055,438,5,057,475,5,096,867,5,064,802,5,132,380,5,189,192,5,321,106,5,347,024,5,350,723,5,374,696 and 5,399,635.All these patents and application are introduced as reference here.

Polymerization is carried out according to Ziegler-Natta or Kaminsky-Sinn class polymeric already known processes.In other words, with monomer and catalyzer in temperature-30 ℃ to 250 ℃, contact at high temperature usually.Polymerization can be carried out under inert gas atmospheres such as shielding gas such as nitrogen, hydrogen, hydrogen, ethene.Known as this area, hydrogen also can be used for controlling molecular weight.Catalyzer can use by itself, or is loaded in suitable carriers such as aluminum oxide, MgCl ₂Or on the silicon-dioxide so that heterogeneous carried catalyst to be provided.Can use solvent if need.Suitable solvent comprises toluene, ethylbenzene and excessive vinylidene aromatic monomer or olefinic monomer.Reaction also can in the suspension that uses perfluorinated hydrocarbon or similar liquids, in the gas phase of using bed bioreactor, or be carried out in the solid phase powder polymerization under solution or slurry conditions.The catalytically effective amount of catalyzer of the present invention and promotor is any amount that successfully causes forming polymkeric substance.This tittle can be measured by the known normal experiment of those skilled in the art easily.But the preferred amounts of catalyzer and promotor should be enough to provide the monomer of addition polymerization: the catalyzer equivalence ratio is 1 * 10 ¹⁰: 1 to 100: 1, preferred 1 * 10 ¹⁰: 1 to 500: 1, most preferably 1 * 10 ¹⁰: 1 to 1,000: 1.The common consumption of promotor should provide promotor: the catalyzer equivalence ratio is 10,000: 1 to 0.1: 1, preferred 1,000: 1 to 1: 1.

The resulting polymers product is by filtering or other method recovery.

Same suitable is the random basically interpolymer with at least one alpha-olefin/binyl aromatic hydrocarbons/vinyl-arene/alpha-olefin four unit group sequences that has in the common pending application (September 4 1996 applying date) that is disclosed in people such as Francis J.Timmers.These interpolymers contain intensity other signals greater than 3 times of peak and peak-to-peak noises.These signals appear in chemical shift 43.75-44.25ppm and the 38.0-38.5 scope.Particularly, observe main peaks at 44.1,43.9 and 38.2 places.Proton test NMR experiment peak shows that the signal in the 43.75-44.25ppm of chemical shift zone is the methine carbon atom, and the signal in regional 38.0-38.5ppm is the mesomethylene carbon atom.

For measuring the C-13NMR chemical shift of these interpolymers, make with the following method and condition.By 50% (volume) unsym.-tetraehloroethane-d ₂With 50% (volume) 0.10M 1,2, the polymers soln of preparation 5 to 10% weight in the mixture that tri acetylacetonato chromium in the 4-trichlorobenzene is formed.NMR composes at 130 ℃ down with reverse stepwise decoupling program, 90 ° of pulse widths and 5 seconds or longer pulse delay acquisition.Spectrum is the separation methylene signals of polymkeric substance to be appointed as 30.000ppm provide as a reference.

It is believed that these new signals are because insert due to the sequence that at least one alpha-olefin forms the front and back of the vi-ny l aromatic monomers that links to each other at two statures-tail, for example by due to ethylene/styrene/styrene/ethylene four unit group sequences, styrene monomer inserts and only occurs in 1,2 (head-tail) mode in the described four unit group sequences.Those skilled in the art know, for this vi-ny l aromatic monomers except that vinylbenzene and the four unit group sequences of the alpha-olefin except that ethene of relating to, ethylene/vinyl base aromatic monomer/vi-ny l aromatic monomers/ethene four unit group sequences will obtain similar C13NMR peak, but chemical shift changes slightly.

These interpolymers are by being under about-30 to about 250 ℃ in temperature, carrying out the polymerization preparation that in the presence of catalyzer of representing such as following general formula and inessential but preferred active cocatalyst described general formula is: Wherein: each C _pExpression and the substituted cyclopentadienyl of M independently with π-key bonding; E is C or Si; M is an IV family metal, preferred Zr or Hf, most preferably Zr; Each R is H independently, contains about at the most 30, preferred 1 to about 20, more preferably 1 alkyl, sila alkyl or silicon alkyl alkyl to about 10 carbon atoms or Siliciumatom; Each R ' is H independently, and halogen contain about at the most 30, preferred 1 to about 20, more preferably 1 alkyl,-oxyl, sila alkyl, silicon alkyl alkyl to about 10 carbon atoms or Siliciumatom, or two R ' groups can form C together _1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2.Suitable substituted cyclopentadienyl comprises those that following general formula is represented:

Wherein each R is H independently, contains about at the most 30, preferred 1 to about 20, more preferably 1 alkyl, sila alkyl or silicon alkyl alkyl to about 10 carbon atoms or Siliciumatom, or two R form the divalent derivative of this group together.R preferably is (comprising all wherein suitable isomer) hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, phenyl or silylation independently, or (if suitable) two this groups are joined together to form fused rings such as indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl, or the alkyl substitutive derivative of these fused rings architecture compounds.

Particularly preferred catalyzer comprises (for example) racemize-(dimethylsilane two bases (2-methyl 4-phenyl indenyl)) zirconium dichloride, racemize-(dimethylsilane two bases (2-methyl 4-phenyl indenyl)) 1,4-phenylbenzene-1,3-butadiene zirconium, racemize-(dimethylsilane two bases (2-methyl 4-phenyl indenyl)) two-C _1-4Alkyl zirconium, racemize-(dimethylsilane two bases (2-methyl 4-phenyl indenyl)) two-C _1-4Zirconium alkoxide or its any mixture etc.

Additive and auxiliary agent can be included in the used polymkeric substance of the present invention to improve required characteristic.Suitable additive comprises pigment, UV stablizer, oxidation inhibitor, whipping agent, lubricant, softening agent, photosensitizers and its mixture.

When preparation contained the interpolymer of vinylidene aromatic monomer, using was not that the alpha-olefin comonomer of being obstructed in special space is suitable.Under the condition of not wishing to be subjected to any particular theory pattern constraint, it is believed that because active sites along with the adding vinyl compound that is obstructed becomes crowded, makes another vinyl compound that is obstructed not enter in the polymerization as the next monomer in the sequence.After adding one or more alkene (rather than the vinyl compound that is obstructed), obtain to can be used for introducing the active sites of vinyl monomer of being obstructed once more.Yet to a certain extent, vinylidene aromatic monomer or be obstructed vinyl monomer in reverse order in the insertion polymerization thing chain promptly causes forming two methylene groups thus between substituted polymer main chain part.

These polymkeric substance preferably have M greater than 13,000, more preferably greater than 20,000, most preferably greater than 30,000.These polymkeric substance also preferably have melt index (I ₂) (ASTM D-1238 program A, condition E) be lower than 125, more preferably 0.01-100, most preferably 0.1 to 10.

Before polymerization, if need, monomer and solvent can be by the vacuum distilling purifying, and/or contact with molecular sieve, silicon-dioxide or aluminum oxide and to remove impurity.In addition, active protection reagent (blanking agent) can be used for removing impurity as trialkylaluminium, basic metal and metal alloy, particularly Na/K.

Composition of the present invention can be by adopting normally used equipment blending in pave the way, put up a house top and other construction work with interpolymer and bituminous material in any conventional manner.Usually, bituminous material is remained under the high temperature (for example 150 to 180 ℃), the random basically interpolymer with predetermined amount grinds in the adding bituminous material with high-shear blending machine (as Silverson, rotating speed 3500-4000rpm) simultaneously.After time, then at high temperature hang down shear-mixed preset time (as under 300rpm, mixing 30 minutes) through predetermined high shear mixing with blade type mixing tank.In addition, composition of the present invention can be by only preparing interpolymer and bituminous material under temperature 150-240 ℃ with low shear-type mixing tank blending.Polymer materials component (B) is used with the pulverulent solids form usually, but also can use in the solution form in solvent such as the toluene, then it is mixed with molten asphalt.Other additive such as filler, sand, stone and in this material normally used other agglomerate can optionally mix with this blend.

When the interpolymer as component of the present invention (B) contains the diolefinic monomer of introducing, usually need and preferably in composition, use cross-linked material component (C), as the cross-linked material of sulphur and/or sulfur-bearing, as methyl tuads, TMTD, dimorpholine based bisulfide, dibutyl xanthogenic acid disulphide or its any mixture.Preferred cross-linking agents is a sulphur.

When the linking agent material was used for the present composition, the amount of the linking agent of use (C) was that about 1 to 20% weight, preferred about 1 is to about 15% weight, 5 to 15% weight (by the amount of component (A)) more preferably from about.

When using component (C) (cross-linked material), itself and component (A) premix can be followed the gained material and component (B) blending, maybe can be with itself and component (A) and pre-composition blending (B).Blending is in temperature about 130 ℃ to about 200 ℃ under each situation, preferred about 150 ℃ to about 190 ℃, more preferably from about carries out under 170 ℃ to about 180 ℃.

Component (A), (B) and composition (C) (wherein component (B) is the random basically interpolymer with diolefinic monomer of introducing) are favourable, are out of question because this blend is excessively crosslinked, can more safely operate thus.Polymeric additive is in the blend of (for example) highly unsaturated SBS triblock polymer (styrene-butadiene-styrene) therein, add too much sulphur and can form highly cross-linked colloidal materials, this material can be attached in technology, storage or the application apparatus.Polymeric constituent of the present invention will only be cross-linked to its degree of unsaturation (i.e. the diene content of during preparation controlling easily), can excessive use sulphur.

Also find, be specially adapted to two performances that the well-formedness that is used as the random interpolymer basically of component (B) of the present invention is subjected to this component to a great extent: alpha-olefin content and melt index I ₂Control.Usually, random basically interpolymer for the ethylene/styrene/diolefine in the compositing range of regulation, material with high ethylene content must have the high-melt index compatible with blend, and the component (B) with low ethylene content must have low relatively melt index to keep other suitable purposes of this blend.

Composition of the present invention can be used for paving the way, put up a house top, waterproof paint etc.

Water dispersion of the present invention or emulsion can prepare by the following method: at first prepare the hot blend of interpolymer and bituminous material, then this blend is scattered in formation water dispersion or emulsion in the water.

The other method for preparing dispersion of the present invention or emulsion is: at first prepare dispersion or the emulsion of bituminous material in water, follow water dispersion or emulsion blending with preformed interpolymer.

Dispersion or the emulsion of bituminous material in water is known and commercially available.

Dispersion or the emulsion of interpolymer in water can be by people such as Walther in U.S. Patent No. 5,574, the description preparation in 091 (the introducing as reference here).

The water dispersion of bituminous material of the present invention and interpolymer is used as rubble sealing agent and slurry sealing agent in paving the way.

The following examples are used to the present invention is described and do not limit the present invention in any way scope.

Below testing method be used for being determined at the various performances of the interpolymer that blend uses.

Alkene and vinylidene aromatic content

Basically the composition of random interpolymer is used ¹³C NMR spectrum according to people such as Oliva at polymer (Macromolecules), 1995 (28), people such as pp4665-4667 and Ren are at polymer, 1995 (28), disclosed method or undertaken among the pp2588-2589 by proton N MR spectrum.

Melt index (I ₂)

According to ASTM D-1238, program A, condition E carries out.

Consistency

A part of polymer-asphalt material blend is poured in 2mm * 42mm aluminum pipe, and in being set in 160 ℃ pressure air oven, placed 72 hours.This pipe is taken out from baking oven, make it be cooled to room temperature, put into dry ice then.When blend reaches dry-ice temperature, aluminum pipe is peeled off from blend, this blend is cut at half place obtain top portion and bottom branch, measure the softening temperature of T﹠B part according to ASTM D-3461-85.If the softening temperature difference of top and bottom thinks then that greater than 2.5 ℃ polymkeric substance and bituminous material are incompatible.

Ductility

Measure according to ASTM D-113-86

Rut (Rutting) parameter

Rut parameter (being expressed as G*/sin d) obtains according to the interim method TP5 (American Association of State HighwayTransportation Officers (AASHTO) provisional method TP5) of U.S. state motorway transport management federation.

Viscosity

Viscosity obtains according to the method for ASTM D-4402-87.

Embodiment 1 preparation interpolymer component (B), ES-1 to ES-10

This goes up random copolymerization body and function (tertiary butyl amino) dimethyl (tetramethyl--η ethylene/styrene interpolymer and ethylene/styrene/ethylidene norbornenyl ⁵-cyclopentadienyl) silane dimethyl titanium (+4) catalyzer and three (pentafluorophenyl group) borine promotor (ratio 1: 1) prepare according to following general method.Combination chain alkane solvents (Isopar-E is available from ExxonChemical Inc.), styrene monomer and the non-essential ethylidene norbornene of aequum are dropped in 21 stirred reactors.If hydrogen is used to control molecular weight, then it is expanded (pressure reduction is represented by δ) in 75mL feed pot adding reactor by differential pressure.Material in the reactor is heated to required temperature, then is saturated to required pressure with ethene.The catalyzer and the promotor of aequum are mixed in Isopar-E or toluene, and gained solution is delivered in the catalyst addition tube and injecting reactor in.

Adding ethene on demand proceeds polymerization.Prepare other catalyzer and promotor (if use) material and it is regularly added in reactor by same way as.After reaching the reaction times, polymers soln is drawn off from reactor and end with Virahol.With hindered phenol antioxygen (IRGANOX ^TM1010, available from Ciba Geigy Corp) add in the polymers soln.In about 120 ℃ vacuum drying oven, place and from polymkeric substance, removed volatile matter in about 20 hours.Record this random basically interpolymer and contain the small amount of amorphous polystyrene homopolymer.

Basically the preparation condition of random interpolymer ES-1 to ES-10 provides in table 1.

Table 1 is the preparation condition of random interpolymer basically

Label	Isopar-E ???(g)	Vinylbenzene (g)	Ethene (Mpa b)	ENB a(ml)	H 2(δMPa b)	Temperature (℃)	Time (min)	Catalyzer (μ mol)	Output (g)
										ES-1	365	461	1.38	0	0	80	20	6.5	67.0
ES-2	361	454	1.21	0	0	80	20	7	63.5
										ES-3	361	458	1.38	0	1.03	80	30	10	95.5
ES-4	361	458	1.38	0	0.689	90	30	12	90.0
										ES-5	361	457	1.03	0	0.689	80	30	8	92.4
ES-6	361	461	1.38	0	1.38	100	32	19	103.9
										ES-7	304	455	1.38	75	0.689	90	30	25	93.0
ES-8	369	450	1.55	0	0	80	20	4.5	59.8
										ES-9	361	458	1.72	0	1.05	80	30	7	90.1
ES-10	361	461	1.72	0	1.38	90	30	8	96.4

A ethylidene norbornene (diolefine) b megapascal (MPa)

Basically random interpolymer ES-11 to ES-12 prepares according to following steps.

In 400 gallons of semicontinuous batch reactors of stirring, prepare polymkeric substance.Reaction mixture comprises hexanaphthene (85% weight) ﹠amp by about 250 gallons; The mixture of iso-pentane (15% weight) and vinylbenzene are formed.Before reinforced, solvent, vinylbenzene and ethylene purification removed anhydrate and oxygen.Remove the inhibitor in the vinylbenzene simultaneously.By removing inert substance with ethene cleaning reaction device.With ethene reactor pressure is controlled to setting point then.Add hydrogen control molecular weight.By the reactor jacket water temperature temperature in the reactor is controlled to setting point.Before the polymerization, reactor is heated to required service temperature, respectively control catalyst component (N-1, the 1-dimethyl ethyl) (1-(1,2,3 for dimethyl, 4,5-η)-2,3,4,5-tetramethyl--2,4-cyclopentadiene-1-yl) silane ammino)) (2-) N)-dimethyl titanium (CAS#135072-62-7) and three (pentafluorophenyl group boron) (CAS#001109-15-5), the flow of modified methylaluminoxane type 3A (CAS#146905-79-5), making its mol ratio is 1/3/5, merges also to add in the reactor.After the beginning, keep under the reactor pressure polymerization being carried out continuously ethene being fed on demand in the reactor.In some cases, hydrogen is fed the reactor upper space to keep mol ratio with respect to ethylene concentration.Reaction stops to add catalyst stream after finishing.From reactor, remove ethene, then about 1000 ppm Irganox*1010 oxidation inhibitor are added in the solution, and polymkeric substance is separated from solution.By with steam stripping or by using devolatilization forcing machine separating obtained polymkeric substance from polymers soln in reactor.For the material of steam stripped, need in the equipment of similar forcing machine, further process to reduce residual moisture and unreacted vinylbenzene.

Sample number into spectrum	The solvent that adds		The vinylbenzene that adds		Pressure		Temperature	The H that adds 2Total amount	Operating time	Polymkeric substance in the solution
											Pound	Kilogram	Pound	Kilogram	Psig	kPa	℃	g	Hour	% weight
	ES-11	841	381	662	300	105	724	60	34	4.9											9.8
ES-12											252	114	1320	599	40	276	60	23	6.5	18.0

Sample number into spectrum	Melt index	The total % weight of vinylbenzene in the polymkeric substance	Talcum amount % weight	Separation method
					ES-11	1.0	48.3	＜3.5	Steam stripped
ES-12	1.8	81.6	＜2.0	Steam stripped

POE is catalyzer and the promotor that the ethylene/octene of preparation is as follows used

Titanium: (N-1,1-dimethyl ethyl) dimethyl (1-(1,2,3,4,5-η)-2,3,4,5-tetramethyl--2,4-cyclopentadiene-1-yl) silane ammino)) (2-) N)-and the dimethyl titanium, CAS#135072-62-7

Three (pentafluorophenyl group) boron, CAS#1109-15-5

The MMAO:CAS#146905-79-5 polymerization

In solution polymerization process with well-mixed CSTR (continuous stirred tank reactor) reactor production ethylene/octene.Each polymkeric substance 1250ppm calcium stearate, 500ppmIRGANOX ^TM1076 and 800ppm PEO Q stable.

Merged into single logistics before ethene and hydrogen all ethene and the hydrogen of separator recirculation (and from) are during adding diluent mixture, described diluent mixture is C ₈-C ₁₀Stable hydrocarbon, for example ISOPAR ^TMThe mixture of-E (available from Exxon Chemical Company) and comonomer 1-octene.

Metal complexes and promotor are merged into single logistics, and be injected in the reactor continuously.Catalyzer is above-described; Main promotor is three (pentafluorophenyl group) borine, available from Boulder Scientific (with at ISOPAR ^TM3% weight solution form the in-E hydrocarbon mixture is used); Inferior promotor is modified methylaluminoxane (MMAO Type 3A), available from AkzoNobel Chemical Inc, with the solution form with 2% weight aluminium in heptane.

Before adding polymerization reactor, keep enough residence time so that metal complexes and promotor reaction.Reactor pressure is constant to remain under about 475psig..

After the polymerization, the logistics that reactor is flowed out adds in the separator, molten polymer is separated from unreacted comonomer, unreacted ethene, unreacted hydrogen and diluent mixture logistics, described mixture stream passes and new comonomer, ethene, hydrogen and thinner merging are recycled in the reactor once more.Subsequently molten polymer is carried out pelletizing of line material or granulation, in water-bath or tablets press, after the cooling, collect solid particulate.Following table has been described the performance of polymerizing condition and resulting polymers.

New ethylene feed speed (Pounds Per Hour) (kilogram/hour)	69 31.30
		Total ethylene feed speed (Pounds Per Hour) (kilogram/hour)	77 34.93
New octene feed rate (Pounds Per Hour) (kilogram/hour)	52 23.59
		Total octene feed rate (Pounds Per Hour) (kilogram/hour)	120 54.43
Total octene concentration (% weight)	11.5
		New hydrogen feed rate (standard cm 3/min)	0
Solvent and octene feed rate (Pounds Per Hour) (kilogram/hour)	1046 474.46
		Conversion of ethylene (% weight)	75.6
Temperature of reactor (℃)	98
		Charge temperature (℃)	15
Catalyst concn (ppm)	79
		Rate of catalyst flow (Pounds Per Hour) (kilogram/hour)	0.237 0.108
Main cocatalyst concentration (ppm)	2288
		Main promotor flow velocity (Pounds Per Hour) (kilogram/hour)	0.265 0.120
Inferior cocatalyst concentration (ppm)	698
		Inferior promotor flow velocity (Pounds Per Hour) (kilogram/hour)	0.137 0.062
Product density (g/cm 3)	0.860
		Polymer melt index (I 2, in the time of 190 ℃)	13

Ethylene/octene density is 0.860 (being obtained by ASTM792), I ₂Be 13 (obtaining), I by ASTM D-1238 ₁₀Be that 92.25 (obtaining by ASTM D-1238), octene content are 43% weight (15.9% mole).

The Baytown AC-10 bituminous material of blend is not available from Exxon.

Table 2 provides the various polymer properties of using in the blend.Table 2 polymer performance

The polymkeric substance label	Styrene content		Melt index (I 2)
				% weight	The % mole
	???ES-1	????36.4				????13.4	????0.05
???ES-2			????39.7	????15.1	????0.08
	???ES-3	????36.3				????13.3	????0.49
???ES-4			????32.0	????11.2	????1.08
	???ES-5	????42.6				????16.7	????0.51
???ES-6			????34.3	????12.3	????7.12
	???ES-7*	????35.3				????14.9	????10.15
???ES-8			????32.9	????11.7	????＜0.05
	???ES-9	????26.5				????8.8	????0.64
???ES-10			????27.7	????9.4	????1.73
	???ES-11	????48.3				????20.1	????1.28
???ES-12			????81.6	????54.4	????1.30

* interpolymer ES-7 contains 35.3% weight (14.9% mole) vinylbenzene, 50.9% weight (80% mole) ethene and 13.8% weight (5.1% mole) ethylidene norbornene.Preparation bituminous material-blend polymer

With Exxon Baytown AC-10 bituminous material heating and remain under 170 to 180 ℃, be used in simultaneously 3500-4000rpm down the Silverson LD-4 high-shear blending machine of running 3.5% (based on pitch+polymer weight meter) ground in the bituminous material.After 30 minutes high shear mixing, the blade type mixing tank that then is used in running under the 300rpm carries out 30 minutes low shear-mixed under 170 to 180 ℃.Sulfur-crosslinked as if polymkeric substance is carried out, then this moment the sulphur of 0.5% weight is added in the polymer-asphalt material blend, and blend is mixed the scheduled time under low the shearing.

Table 3 provides the performance and the blend performance of polymer samples.Table 3 polymkeric substance and pitch (Exxon Baytown AC-10 pitch) blend performance

The sample label	Polymkeric substance			Blend
										Type	I 2	Vinylbenzene % weight	Polymkeric substance % in the blend	135 ℃ of viscosity @ (cp/Pa)	S.H. R.P. b(G */sinδ)	Softening temperature (top/end) ℃	Consistency	Ductility (4 ℃ of cm)
	1	ES-1	0.05	36.4	3.5	3035/3.035	5390	71.5/70.9	Be										32.5
2										ES-2	0.08	39.7	3.5	3485/3.485	3790	63.9/63.8	Be	35.3
	3	ES-3	0.49	36.3	3.5	1240/1.240	2710	69.8/68.1	Be										36.4
4										ES-4	1.08	32.0	3.5	1193/1.193	2610	76.1/73.9	Be	26.6
	5	ES-5	0.51	42.6	3.5	1208/1.208	3080	54.6/53.2	Be										28.9
6										ES-6	7.12	34.3	3.5	650/0.650	3000	64.3/64.3	Be	27.1
	7	ES-11	1.28	48.3	3.5	920/0.920	2392	51.9/51.9	Be										24.8
8										ES-12	1.30	81.6	3.5	430/0.430	1667	47.3/47.3	Be	7.0
	A **	Do not have	Na c	n a	0	280/0.280	919	na c	na c										7.5
B **										ES-8	＜0.05	32.9	3.5	3105/3.105	3560	76.6/71.8	No	36.7
	C **	ES-9	0.64	26.5	3.5	1350/1.35	2780	80.2/75.6	No										21.1
D **										ES-10	1.73	27.7	3.5	990/0.990	N.D. d	81.3/74.1	No
	E **	POE	13	Na c	3.5	650/0.650	2410	52.7/49.8	No										7.3

* is not embodiments of the invention a Brookfield (Brookfield) viscosity b S.H.R.P.=motorway design studies scheme (Strategic Highway ResearchProgram), the inapplicable d undetermined of rut parameter c na=

Table 3 explanation is not that the random basically interpolymer of all ethylene/styrene all is suitable as asphalt modifier.All ethylene/styrene basically random interpolymer compatible with pitch has improvement performance (comparing with unmodified AC-10 pitch) (sample A, no polymkeric substance).

If use the too low polymkeric substance of melt index, then sacrifice consistency (seeing sample B).Do not wishing to be subjected to it is believed that this phenomenon of polymer modifiers molecular weight control under the particular theory constraint.Reduce with melt index, polymericular weight increases, and the blend performance improves simultaneously.The polymkeric substance that molecular weight is too high causes incompatible polymer-bitumen blend.

As can be seen from Table 3, the styrene content in the random basically interpolymer of ethylene/styrene is significant variable equally, and reason is the performance and the consistency of polymer modifiers in pitch of its control blend.Under low-styrene-content, have the random basically interpolymer that can compare consistency and provide improved blend performance: show (comparative blend 3 and 5 and blend 7 and 8) by rut parameter (S.H.R.P.), softening temperature and ductility.Yet,, sacrificed consistency (comparative blend 3 and 5 and C) along with styrene content becomes too low.Preparation cross-linked bitumen material-ES sample blend

With Exxon Baytown AC-10 bituminous material heating and remain under 170 ℃, with Silverson Model high-shear blending machine the random basically interpolymer or the former abrasive lapping of comparative polymer of the 3.5% weight amount of giving are gone in the bituminous material simultaneously.Temperature is remained under 160 ℃, and this moment, the sulphur (based on pitch+polymkeric substance+sulphur meter) with 0.5% weight added in the polymer-asphalt material blend, and this blend is mixed the scheduled time under low the shearing.

Table 4 provides blend mixing time, uncrosslinked and crosslinked blends and as the polymer properties of component (B)

Table 4 cross-linked bitumen blend performance

The blend label	Polymkeric substance in the blend		Sulphur mixing time (min.)	Viscosity a(cps,135℃)	Softening temperature (℃)	S.H.R.P. (G*/sinδ)
							Type	% weight
	XLB-1	ES-7							3.5	0 b	568	47.5	1610
XLB-2			ES-7	3.5	30	670	48.9	1920
	XLB-3	ES-7							3.5	180	N.D. c	N.D. c	3580

The uncrosslinked c undetermined of a brookfield viscosity b

Table 4 provides the effect of sulfur-crosslinked asphalt-polymer blend.The crosslinked softening temperature of blend that causes very in a small amount increases and rut parameter (S.H.R.P.) increase, relatively XLB-1 and XLB-2.Long crosslinking time causes crosslinked increase (advantageously increasing demonstration by rut parameter (S.H.R.P.)), relatively XL-2 and XL-3.Compare with uncrosslinked blend XLB-1, crosslinked blends XLB-2 and XLB-3 have improved rut parameter (S.H.R.P.).Embodiment 2 preparation labels are that ES-13,14,15,17,18 and 19 E/S interpolymer reactor are described

The single reactor that uses is 6 gallons (22.7L), oil jacket, continuously stirring autoclave reactor (CSTR).Magnetic coupling agitator with Lightning A-320 blade is used for mixing.(3,275kPa) operate by the following liquid of expiring at 475psig for this reactor.Feed stream adds from the bottom, discharges from the top.Heat-transfer oil circulates to remove some reaction heat through reactor jacket.It after reactor outlet the fine motion under meter of a measurement logistics and solution density.It is also heat insulation that all pipelines of reactor outlet all use 50psi (344.7kPa) steam to follow the tracks of.

Catalyst component

The polymkeric substance label	Titanium compound (catalyzer) type	Boron compound (promotor)		MMAO (inferior promotor) Al/TI ratio
					Type	Boron/Ti ratio
		ES-13	A a				A c	1.25	10
ES-14	A a			A c	1.25	10
		ES-15	A a				A c	1.25	10
ES-16	B b			A c	1.25	6
		ES-17	B b				A c	1.25	6
ES-18	B b			A c	1.25	6

A has following structure C ₂₆H ₃₅NSiT437.53 g/moC, 71.4%H, 8.1%N, 3.2%Si, 6.4%Ti, 10.9%b (tertiary butyl amino) dimethyl (tetramethyl-ring pentadienyl) silane 1,3-pentadiene closes titanium (II) c long-chain ammonium borate salt mixture (C18-C22).Step

Ethyl benzene solvent is descended in the input packaged unit at 30 psig (207 kPa).The raw material that adds reactor is by fine motion (Micro-Motion) streams flowmeter measurement.With the variable surge pump control feed rate of speed.One effluent is set so that the flushing logistics to catalyst injection pipeline (1 Pounds Per Hour (0.45 kilogram/hour)) and reactor agitator (0.75 Pounds Per Hour (0.34 kilogram/hour)) to be provided in the solvent pump exit.These logistics are measured with differential pressure flowmeter and are saved the gate control of miniflow needle type valve by hand adjustment.Under 30psig (207kPa), in this packaged unit, add the styrene monomer of removing stopper.The raw material microfauna materials flow flowmeter measurement that adds reactor.With the variable surge pump control feed rate of speed.Styrene stream is mixed with remaining solvent stream.With ethene 600psig (4,137kPa) down in the feeding packaged unit.Before the Research flow control valve, use microfauna materials flow flowmeter measurement ethylene streams immediately.Hydrogen is fed in the ethylene stream in ethene control valve exit with Brooks under meter/controller.Ethene/hydrogen mixture and solvent/styrene stream are at room temperature merged.Temperature when solvent/monomer adds reactor is reduced to about 5 ℃ by the interchanger of the glycol of having on chuck-5 ℃.This logistics enters reactor bottom.Three component catalyst systems and its rinse solvent are also in the bottom but enter reactor through the mouth different with monomer stream.The preparation catalyst component carries out in inert-atmosphere glove box.Be full of the component input of dilution in the barrel of nitrogen and be dropped in the catalyzer operation still in the process island.Catalyzer is pressurizeed by piston pump and with microfauna materials flow flowmeter measurement flow from this operation still.These logistics before entering in the reactor, single injection pipeline are being merged mutually and with the catalyzer rinse solvent immediately.

By HP catalyst killer (water mixed solvent) is added in the reactor product pipeline behind fine motion flowmeter survey solution density.Other polymeric additive can add with HP catalyst killer.In pipeline, provide static mixer, so that HP catalyst killer and additive are disperseed in reactor effluent stream.Then with in this logistics input post-reactor well heater, this well heater is provided for desolventizing the additional energy of flash distillation.When fluid flows out the post-reactor well heater, and reactor pressure control valve place pressure from 475psig (3, flash distillation appears when 275kPa) reducing to about 250mm pressure absolute value.The polymkeric substance of this flash distillation enters in the hot-oil jacket devolatilizer.About 85% volatile matter is removed from polymkeric substance in devolatilizer.This logistics through the condensation of glycol chuck interchanger, is entered the vacuum pump suction, and is discharged in glycol chuck solvent and the styrene/ethylene separator.Solvent and vinylbenzene are removed from the separator bottom, and ethene is removed from the separator top.Decide ethylene streams and analyze its composition with fine motion mass flow instrumentation.The observed value of emptying ethene adds that the dissolved gases calculated value can be used for calculating conversion of ethylene in the ethylene/styrene logistics.Extract isolating polymkeric substance in the devolatilizer out with toothed gear pump, and it is sent in the ZSK-30 devolatilization vacuum-extruder.This exsiccant polymkeric substance draws off with single line material form from forcing machine.This line material cools off when water-bath is extracted out.From the line material, blow away too much water with air, and this line material is cut into pellet with line material cutting machine.

The polymkeric substance label	Temperature of reactor ℃	Solvent flux		The ethene flow		Hydrogen flowing quantity SCCM*	The vinylbenzene flow		Transformation efficiency %
										Pounds Per Hour	Kilogram/hour	Pounds Per Hour	Kilogram/hour	Pounds Per Hour	Kilogram/hour
		ES-13	90.2	29.9	13.57		2.9	1.32								20.9	9.0	4.09	91.9
ES-14	84.1					28.4			12.89	2.3	1.04	16.0	10.5	4.77	92.8
		ES-15	73.7	13.5	6.13		1.2	0.54								9.0	12.0	5.45	87.1
ES-17	73.6					17.2			3.55	1.5	0.68	2.7	12.0	5.45	82.5
		ES-18	90.6	23.4	10.62		2.0	0.91								2.8	14.0	6.35	85.6
ES-19	105.2					29.1			13.21	3.0	1.36	5.0	9.0	4.09	89.0

* standard cubic centimeter per minute

The preparation label is the E/S interpolymer of ES-16

The identical data for preparing ES-11 and 12 among step and the embodiment 1 provides in following table

Sample number into spectrum	The solvent that adds		The vinylbenzene that adds		Pressure		Temperature ℃	The total H that adds 2The gram number	Operating time hour	Polymkeric substance in solution, % weight
											Pound	Kilogram	Pound	Kilogram	psig	?kPa
	ES-16	252	114	1320	599	42											290	60	0	2.8	11.5

Sample number into spectrum	Melt index	The total % weight of vinylbenzene in the polymkeric substance	Talcum total amount % weight	Separation method
					ES-16	0.18	81.7	＜2.5	Steam stripped

The feature of polymkeric substance provides in table 5

Table 5

The polymkeric substance label	Vinylbenzene %		Melt index I 2g/10min.	APS c
					Always a	Polymkeric substance b
	% weight	% weight
					ES-13	44	43	1.0	＜3
ES-14	57.2	56	1.08	＜3
					ES-15	～75	68.2	1.16	＜10
ES-16	81.7	72.5	0.18	8.6
					ES-17	56.5	51	0.4	～9
ES-18	46.5	37	0.6	13
					ES-19	31	23.4	1.08	7.5

The cinnamic amount of a in interpolymer adds the vinylbenzene amount in random isotactic polystyrene.The amount of the random isotactic polystyrene in the polymkeric substance that generates in the vinylbenzene amount c reactor in the b interpolymer.The consistency of E/S interpolymer in pitch

Pitch is naturally occurring or obtains as the form of crude oil refining byproduct.The composition of crude oil and rock asphalt alters a great deal according to geographic origin.Therefore, no matter any bituminous physicals is that make or natural, all significantly different mutually.

Owing to bituminous chemistry complicacy, therefore can not only predict the interaction/consistency of pitch and polymkeric substance or other properties-correcting agent based on chemical constitution.Equally, can not be based on the interaction that is generally used for characterizing bituminous molecular characterization (bituminous matter, aromatic compound, saturate, resin) prediction polymkeric substance or other properties-correcting agent in the past.

For defining the compositing range of the desirable interpolymer of acquisition and various bituminous composition excellent compatibility better, prepare the blend that contains 4% interpolymer below in each pitch.

In compatibility test, used various pitches are as follows:

Citgo AC-10: by the Venezualan of Cities Service Company production

The pitch of crude production

Murphy 120-150: by the N.W.Canadian of Murphy Oil Co. production

The pitch of crude production

Fina AC-10:FINA Oil﹠amp; The West Texas Sour that Chemical Co. produces

The pitch that Crude crude oil (WTS) is produced

DS AC-10: in the middle of the West Texas by Diamond Shamrock production

The pitch that body crude oil (WTI) is produced

Marathon AC-10: by the Arabian heavy crude oil of Marathon Oil Co. production

The pitch of producing

Conoco AC-10: by the Wyoming Sour crude oil of Conoco Oil Co. production

(WY) pitch of Sheng Chaning

For all interpolymer samples that provide in the table 6, by using low shearing blade agitator and under 450F, mixing preparation in 2 hours and bituminous blend.For the SBS sample that provides in the table 6, with the bituminous blend by under 375F, mix preparation in 2 hours with high-shear Silverson mixing tank.Industrial being generally used for of high-shear mixer is blended into the SBS polymkeric substance in the pitch.SBR sample (as shown in table 6) was mixed 1 hour with the pitch blending and under 325 °F with the low blade agitator of shearing.The consistency of polymkeric substance/bitumen blend is measured according to preceding method.The value that table 6 provides is that the softening temperature of blend top and blend bottom is poor.The softening temperature difference is suitable for a short time, wherein about 10 of differences or lower be preferred.The big expression polymkeric substance of softening temperature difference separates from pitch, and this is inappropriate.The result of compatibility test provides in table 6.

Table 6

Polymkeric substance		The softening temperature difference, the top/end
														Label	Vinylbenzene % weight among the E/S	Venez Citgo AC-10		Canadian Murphy 120-150		WTS?Fina AC-10		WTI?DS AC-10		Arab?Hvy Marathon AC-10		WY?Sour Conoco AC-10
°F	℃	°F	℃	°F	℃	°F	℃	°F	℃	°F	℃
												ES-19	23.4			51	28.3	52	28.9	57	31.7	42	23.3	59	32.8	44	24.4
ES-18	37	13	7.2	23	12.8	0	0	3	1.7	15	8.3			2	1.1
												ES-13	43			1	0.6	9	5.0	1	0.6	1	0.6	5	2.8	20	11.1
ES-17	51	8	4.4	8	4.4	4	2.2	9	5.0	10	5.6			10	5.6
												ES-14	56			19	10.6	7	3.9	4	2.2	0	0	6	3.3	23	12.8
ES-15	68.2	51	28.3	2	1.1	1	0.6	4	2.22	21	11.7			34	18.9
												ES-16	72.5			41	22.8	78	43.3	4	2.2	4	2.22	88	48.9	89	49.4
SBS*	---	55		13		3		7		9				57
												SBR*	---			82		85		5		13 3		88		82

* not embodiments of the invention

Analytical data proves to have best consistency by the interpolymer (ES-18, ES-13, ES-17 and ES-14) of various types of asphalt test vinylbenzene % weight in the 37-56% scope.The sample ES-19 that only has 23.4% low relatively % weight styrene has the bitumen compatibility of non-constant.Similarly, also proof has suitable high-phenylethylene % weight respectively, promptly 68.2% much has the consistency of being on duty mutually in the asphalt tests with 72.5% sample ES-15 with ES-16.

Be also noted that with SBS and compare, prove that equally interpolymer sample ES-18, ES-13, ES-17 and ES-14 and all kinds pitch have fabulous consistency with SBR.The industrial asphalt modification that is widely used in of SBS and SBR sample, but need to use auxiliary compatilizer (as oil) usually to obtain the blend of shelf-stable.Data presentation in the table 6 under many circumstances, does not use auxiliary compatilizer should obtain the pitch/inter-polymer blends of shelf-stable.

It also is favourable in the pitch that interpolymer can be blended under not using high-shear mixer, because this has significantly reduced the cost of blending equipment.Super shop (Superpave) classification of motorway design studies scheme (SHRP)

The following determination of test method of super shop grade separation:

1. dynamic shear rheometer-AASHTO method TP-5

2. roll-in Thin Film Oven Test TFOT (Rolling Thin Film Oven Test)-AASHTO method T-240

3. pressure aging device (Pressure Aging Vessel)-AASHTO method PP1

4. curved beam rheometer (Bending Beam Rheometer)-AASHTO method TP-1

5. Brookfield melt viscosity-ASTM D-4402

6. flash-point-AASHTO method T-48

The grade separation of various ethylene/styrene interpolymer-bituminous compositions provides in table 7.High and low use temperature (℃) represent that first value is positive number, second value is negative; Be suitable for classification 70-22 and be meant 70 ℃ of high temperature gradings and low use temperature-22 ℃.(temperature survey is only undertaken by 6 ℃ of increases, as stipulating in the rule of the super shop of SHRP).Therefore, high temperature grading 76 is more suitable than classification 70, and low temperature classification-28 is more suitable than classification-22.

Usually, the data declaration in the table 7, the super shop grade separation of interpolymer modifying asphalt equal or are better than under many circumstances the super shop of the bituminous grade separation of corresponding SBS or SBR (representing the polymkeric substance of present industrial use) modification.In addition, as can be seen, have the super shop grade separation of the sample ES-15 generation of 68.2% weight styrene than other interpolymer sample difference.

Table 7

Polymkeric substance		Super shop classification a
								Label	Vinylbenzene % among the E/S	Canadian Murphy 120-150	WTS fina AC-10	WTI DS AC-10	Arab?Hvy Marathon AC-10	Venez Citgo AC-10	WY?Sour Conoco AC-10
No *	---	58-22	58-16	58-22	58-28	64-28	58-28
								ES-19	23.4	72-28	70-22	70-22	76-22	76-28	76-22
ES-18	37	70-28	70-22	70-22	76-28	76-28	76-28
								ES-13	43	70-22	70-22	70-22	76-28	76-22	76-22
ES-17	51	70-22	70-22	64-22	76-28	76-28	76-22
								ES-15	68.2	64-22	64-22	64-22	70-22	70-22	70-22
SBR b	---	70-22	64-28	64-28	70-28	70-28	76-28
								SBS c	---	70-22	64-22	64-22	70-28	70-28	70-22

* be not the high and low use temperature of embodiments of the invention a (℃) in first value be positive number, second value is negative; Be suitable for classification 70-22 and be meant 70 ℃ of high temperature gradings and low use temperature-22 ℃.(temperature survey is only undertaken by 6 ℃ of increases, as stipulating in the rule of the super shop of SHRP).B uses available from the styrene butadiene rubbers of Textile Rubber Co. (as UltrapaveUP-70) and replaces the E/S interpolymer.C uses available from the styrene-butadiene-styrene block copolymer of Shell Chemical (as Kraton D-1101, a kind of linear styrene-butadiene-styrene block copolymer with styrene content 30% weight) and replaces the E/S interpolymer.The Δ T of the mixture of pitch and E/S interpolymer

Δ T value defined is the absolute difference between the temperature of the temperature of bituminous cement when just satisfying the super shop of pitch high temperature class requirement when just having passed through the low temperature class requirement with it.These are measured the super usually shop rule that does not adopt 6 ° of intervals and carry out.Higher Δ T value is suitable, because the expression bituminous cement has the use temperature scope of broad.

The Δ T value of various polymer-asphalt compositions provides in table 8.Except ES-15 (68.2% weight styrene), to compare with the pitch of SBR modification with using at present commercial polymer modifiers SBS mutually, the interpolymer sample all shows higher Δ T value in the bituminous cement blend.Table 8

Polymkeric substance		Δ T value; ℃
								Label	Vinylbenzene % among the E/S	Canadian Murphy 120-150	WTS fina AC-10	WTI DS AC-10	Arab?Hvy Marathon AC-10	Venez Citgo AC-10	WY?Sour Conoco AC-10
No *	---	87	88	84	91	95	91
								ES-19	23.4	101	98	98	105	108	105
ES-18	37	103	99	101	105	109	107
								ES-13	43	98	94	99	106	105	104
ES-17	51	100	97	93	106	107	106
								ES-15	68.2	86	90	87	96	99	97
SBR b	---	95	96	93	101	104	112
								SBS c	---	95	95	95	101	104	101

* be not the high and low use temperature of embodiments of the invention a (℃) in first value be positive number, second value is negative; Be suitable for classification 70-22 and be meant 70 ℃ of high temperature gradings and low use temperature-22 ℃.B uses available from the styrene butadiene rubbers of Textile Rubber Co. (as UltrapaveUP-70) and replaces the E/S interpolymer.C uses available from the styrene-butadiene-styrene block copolymer of Shell Chemical (as Kraton D-1101) and replaces the E/S interpolymer.

Numerical value in the table 6,7 and 8 clearly illustrates, for polymer content is the pitch of 4% weight and the mixture of ethylene/styrene interpolymer, has styrene content about 37 to the ethylene/styrene interpolymer (partly containing ethene and vinylbenzene resistates at interpolymer) of about 56 (the vinylbenzene % in the interpolymer) various bituminous compositions are had suitability.

Suitability is defined as has excellent compatibility/package stability simultaneously in various bituminous compositions, meanwhile, compare with the blend that identical pitch obtains with the polymkeric substance of present industrial use, the bituminous cement that obtains according to the present invention has equal or better SHRP super shop grade and Δ T value.

Claims (18)

1. a random basically interpolymer comprises

(1) about 30 to about 80% weight derived from least a polymer unit with alkene of 2 to 10 carbon atoms;

(2) about 20 polymer units derived from one or more vinylidene aromatic monomers to about 80% weight; With

(3) about 1 has the polymer unit of the diolefine of 4 to 10 carbon atoms to about 20% weight derived from one or more;

The percent of total sum of component (1), (2) and (3) is 100.

2. the random basically interpolymer of claim 1, wherein component (1) is the polymer unit of derived from ethylene.

3. the random basically interpolymer of claim 1, wherein component (2) is derived from cinnamic polymer unit.

4. the random basically interpolymer of claim 1, wherein component (3) is the polymer unit derived from ethylidene norbornene.

5. the composition of claim 1, wherein component (1) is the polymer unit of derived from ethylene, component (2) is derived from cinnamic polymer unit, and component (3) is the polymer unit derived from ethylidene norbornene.

6. a blend comprises

(A) about 80 bituminous material to about 99% weight; With

(B) the about 1 at least a interpolymer to about 20% weight, described interpolymer contain about 20 and have 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and about 20 to about 80% weight.

7. the blend of claim 6, wherein

(a) amount of component (A) is about 90 to about 99% weight;

(b) amount of component (B) is about 1 to about 10% weight;

(c) component (B) is a kind of interpolymer, comprises (1) about 20 and has 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and (2) about 20 to about 80% weight.

8. the blend of claim 6, wherein

(a) amount of component (A) is about 99 to about 95% weight;

(b) amount of component (B) is about 1 to about 5% weight;

(c) component (B) is a kind of interpolymer, comprises (1) about 20 and has 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and (2) about 20 to about 80% weight.

9. the blend of claim 6, wherein component (B1) is that vinylbenzene and component (B2) are ethene.

10. the blend of claim 7, wherein component (B1) is that vinylbenzene and component (B2) are ethene.

11. the blend of claim 8, wherein component (B1) is that vinylbenzene and component (B2) are ethene.

12. the blend of claim 6, wherein

(a) amount of component (A) is about 90 to about 99% weight;

(b) amount of component (B) is about 1 to about 10% weight; With

(c) component (B) is a kind of interpolymer, comprise (1) about 25 to about 60% weight derived from cinnamic polymer unit and (2) about 40 polymer unit to the derived from ethylene of about 75% weight.

13. the blend of claim 6, wherein

(a) amount of component (A) is about 95 to about 99% weight;

(b) amount of component (B) is about 1 to about 5% weight;

(c) component (B) is a kind of interpolymer, comprise (1) about 30 to about 55% weight derived from cinnamic polymer unit and (2) about 45 polymer unit to the derived from ethylene of about 70% weight; With

Wherein the melt index that has of component (B) is determined as 0.05 to 5.0g/10min by ASTM D-1238 program A condition E (190 ℃/2.16 kilograms weight).

14. the blend of claim 6, it also contains (C) based on component (A), (B) and total amount meter (C), and consumption is about 0.1 sulphur or sulfur-bearing cross-linked material to about 10% weight; And component (B) is a kind of random basically interpolymer, comprises about 79 to polymer unit, about 69 polymer unit and about 1 the polymer units derived from one or more diolefine to about 20% weight derived from one or more vinylidene aromatic monomers to about 20% weight of about 30% weight derived from one or more alkene.

15. the blend of claim 14, wherein component (B1) is an ethene, and component (B2) is a vinylbenzene, and component (B3) is an ethylidene norbornene; And component (C) is a sulphur.

16. the blend of claim 14, wherein component (B) is crosslinked by component (C).

17. the blend of claim 15, wherein component (B) is crosslinked by component (C).

18. water dispersion or emulsion comprise

(A) about 90 bituminous material to about 99% weight; With

(B) the about 1 at least a interpolymer to about 10% weight, described interpolymer contain about 20 and have 2 polymer units to the aliphatic olefin of about 10 carbon atoms to about 80% weight derived from least a derived from the polymer unit of at least a vinylidene aromatic monomer and about 20 to about 80% weight;

Form water dispersion or emulsion with the water blending.